Acetonyl alkylbenzyl dialkyl ammonium salts



Patented July 29, 1952 .i UNITsD STATES PATENT OFFICE ACETONYLALKYLBENZYL DIALKYL AMMONIUM SALTS Sidney Melamedflhiladelphia, anawmardJ. Croxall, Bryn Athyn, Pa., assign'ors to Robin" & HaasCompamy,*Philadelphia, Pa acorporation of Delaware No Drawing.

Application January 4, 1951', Serial No. 204,482 a 8 Claims. (01. ace-7.6)

This invention relates nium salts of the structure to quaternary ammo- RR! RI! wherein an alkyl groupof eight to sixteen The same end result-isachieved by hydrating dimethylaminopropyne or diethylam-inopropyne (cf.J. Chem.- Soc. 1949, 782) .We havediscovered that reaction of the abovedialkylaminoa'cetones' with alkylbenzyl halides yields valuablelquaternary ammonium salts which are characterized by an unusualcombination of properties.

Suitable alkylbenzyl halides which include also alkylmethylbenzyl andalky-ldimethyl-benzyl =halides; are available through theha-lomethylation of alkylbenzenes in which the alkylgroupcontainseight-to; sixteen carbon atoms and preferably nine ito sixteencarbon atoms. The alkyl group 'can 'be of straight or branched chainstructure. Particularly useful and economical are alkyl groups obtainedfrom propylene polymers, fractions of which can be taken to give groupspredominantly of 9, 12, or carbon atoms. Another economical source of along-chained alkyl group is from close-cut fractions of kerosene, afraction having an average size of 14 carbon atoms being quitedesirable.

Useful starting hydrocarbons are alkylated benzenes, toluenes, andxylenes', which include n-octylbenzene, n-octyltoluene, n-octylxylenes,2- ethylhexylbenzene, 1-methylheptyltoluene, (1,3-dimethyl-l-propylbutyl) benzene, 3,5,5 -trimethylhexyl) -benzene, (3,5,5trimethylhexyDtoluene, (3,5,5-trimethylhexyl) -xylene. nonyltoluene (thenonyl group being from propylene trimer), decylbenzene,n-dodecylbenzene, dodecylbenzene or dodecyltoluene (the dodecyl groupbeing from' propylene tetramer), tetradecylbenzene, tetra decyltoluene,tetradecyldimethylbenzene, pentadecylbenzene, hexadecylbenzene, etc.These are halomethylated with a hydrogen halide and formaldehyde or'paraformaldehyde or with the equivalent thereof conveniently in the'presence' of such a catalyst as zinc chloride in glacial acetic acid.There are thus obtained the chloromethyl or bromomethyl derivatives.

An alkylbenzyl halide and dimethylaminoacetone or diethylaminoacetoneare mixed in) about molar proportions andreacted together'to givequaternary ammonium compounds. The reactionis desirably accomplished inthe presence of a solvent; such as benzene, toluene, isopropylalcohol",- isopropyl ether, acetonitrile, formamide nitromethane, or thelike. Heating is useful in accelerating and/or completing thereaction,temperatures of 50 to 125 C. beinggener-ally suitable; The product isobtained as a-residue upon evaporation of solvent, if used. The residuemaybe purified by stripping, extraction. or similaroperation, ifdesired. I 1

p The preparations of typicalquaternary ammonium salts of this inventionis illustrated by: the

iollowingexamples, in which parts are by weight.

" Era mailed There were mixed 48 parts of octylbenzylchloride, 20.2parts ofdimethylaminoacetone,.and 120 partsof dry benzene. The mixturewas heated under reflux for fourv hours, after which time it Was foundthat the titratable nitrogen was essentially zero. The solvent wasdriven oil to yield a viscous syrup. This was found to contain 3.9% ofnitrogen'and'10.1%'of chlorine and 7 to correspond in composition tooctylbenzylacet onyl dimethyl ammoniuin chloride; for which thecontentsare theoretical nitrogen and chlorine 4.1% and 10:4%, respectively.

This compound is readily soluble in water and:

is compatible with alkaline cleaning solutions.

, It has a phenol coefficient of against -S'ta'phylococcus aurcu s;

Example 2 There were mixed 28 parts of a nonyldimethylbenzyl chloride,13 parts of diethylaminoacetone, and parts of toluene. The mixture washeated under reflux for five hours. The toluene was removed by heatingof the mixture under reduced pressure to yield a gummy residue. Thiscorresponds in composition to nonyldimethylbenzyl acetonyl diethylammonium chloride. It has a 3 phenol coefficient of 315 againstStaphylococcus aureus and of 225 against Salmonella typhosa. Thiscompound has the formula CnHia CzHs C2H5 0111- o HzooHa Example 3 Thiscompound is readily soluble in water. It gives a phenol coefficient of335 against Staphylococcus aareus and of 240 against Salmonella typhosa.

Example 4 A mixture of 17 parts of dimethylaminoacetone, 51 parts of2-methyl-5-dodecy1benzyl chloride, and 120 parts of dry benzene washeated under reflux for three hours. A sample titrated for basicnitrogen showed that the reaction was essentially complete.Concentration under re-' duced pressure gave a quantitative yield ofproduct in the form of a hygroscopic glass. Analysis of this materialshowed the presence of 8.6% of chlorine and 3.5% of nitrogen. Itcorresponds in'composition to dodecylmethylbenzyl dimethyl acetonylammonium chloride, for which the theoretical chlorine content is 8.66and the theoretical nitrogen content is 3.42%. It has a phenolcoeflicient of 375 against Salmonella typhosaand of 640 againstStaphylococcus aureus.

Dodecylbenzyl dimethyl acetonyl ammonium chloride is prepared fromdodecylbenzyl chloride and dimethylaminoacetone as above. It hasproperties very closely similar to those of the dodecylmethylbenzylcompound having phenol coefiicients at least as high as those of thelatter.

Example 5 By the procedure of Example 4- there are reacted 17 parts ofdimethylaminoacetone and 5'7 parts of a pentadecylbenzyl chloride inwhich the pentadecyl group was derived from a propylene polymer cut withabout 15 carbon atoms in the molecule. The product is pentadecylbenzyldimethyl acetonyl ammonium chloride. It has a phenol coefi'icient of 600against Staphylococcus aureus and 395 against Salmonella typhosa.

The alkylbenzyl acetonyl dialkyl ammonium halides of this invention havenot only good bac- There were mixed 29.7 parts of nonylbenzyl tericidalproperties but also other significant and favorable characteristics. Forexample, they remain highly effective in hard water and in the presenceof organic contaminants. This is a distinct advantage over manyotherwise efiective quaternaries. The compounds of this .inventionpossess good solubility coupled with a favorable stability and it is ofinterest that the solubilizing group which is here present is notantagonistic to the action of the ammonium group as is often the case.The constituent parts and their particular configuration providecompounds which are advantageous with regard to properties and at thesame time are advantageous because they are obtained from readilyavailable and economical starting materials.

We claim: 1. As new chemical substances, compounds of the formula R R. R

wherein R is an alkyl group of eight to sixteen carbon atoms, X and Yare members of the class consisting of hydrogen and the methyl group, Rand R" are alkyl groups of not over two carbon atoms, and Z is a memberof the class consisting of chlorine and bromine.

2. As new chemical substances, compounds of the formula )3. CH3 CH3wherein R. is an alkyl group of nine to sixteen carbon atoms.

3. As new chemical substances, compounds of the formula R CH3 CH3 benzyldimethyl acetonyl ammonium chloride. I

'SIDNEY MELAM'ED.

WILLARD J. CROXALL.

REFERENCES CITED The following references are of recordin the file ofthis patentf Stevens: J. Chem. Soc. (London), 1930, pp. 2119-2125. v

1. AS NEW CHEMICAL SUBSTANCES, COMPOUNDS OF THE FORMULA